CN110176593A - A kind of preparation method of the nickelic tertiary cathode material of double-coating - Google Patents
A kind of preparation method of the nickelic tertiary cathode material of double-coating Download PDFInfo
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- CN110176593A CN110176593A CN201910477550.5A CN201910477550A CN110176593A CN 110176593 A CN110176593 A CN 110176593A CN 201910477550 A CN201910477550 A CN 201910477550A CN 110176593 A CN110176593 A CN 110176593A
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The present invention provides a kind of preparation method of the nickelic tertiary cathode material of double-coating, includes the following steps, S1, mixes nickelic ternary precursor with lithium source, and be put into high temperature furnace and calcine, obtains nickelic tertiary cathode material；S2, covering is mixed and is ground with the nickelic tertiary cathode material in step S1, and be put into high temperature furnace and calcine, obtain compound；S3, compound and graphene nanobelt are weighed by certain mass ratio, weighed compound is mixed with ethanol solution, obtained mixed solution A, while weighed graphene nanobelt being mixed with ethanol solution, obtain mixed solution B；Mixed solution B is slowly added into mixed solution A, mixed solution C is obtained；S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic tertiary cathode material of double-coating can be obtained.The present invention surface residual alkali amount of nickelic tertiary cathode material and pH after double-coating are reduced, while the high rate performance of material gets a promotion.
Description
Technical field
The invention belongs to positive electrode preparation technical fields, and in particular to a kind of nickelic tertiary cathode material of double-coating
Preparation method.
Background technique
In recent years, lithium ion battery was unique as a kind of novel high voltage, the rechargeable battery of high-energy density
Physically and electrically chemical property has extensive civilian and national defense applications prospect, and wherein anode material for lithium-ion batteries is that its is heavy
The component part wanted, specific capacity largely determine the energy density of entire battery, the nickelic positive electrode of stratiform
LiNixCoyMn1-x-yO2(x >=0.6) has the advantage of height ratio capacity, high rate capability and low cost, but when nickel content is higher,
Higher to the sensitivity of moisture, the easier moisture absorbed in air makes particle surface form LiOH/Li2CO3Impurity,
And then the surface p H of positive electrode is increased, the processing performance of positive electrode is influenced, while influencing the performance of material capacity, so that
Irreversible capacity increases, and moreover, is easy to produce gas in battery charge and discharge process, so as to cause the security performance of whole system
It is greatly reduced；The LiOH/Li on surface simultaneously2CO3Impurity is easy to react with the byproduct HF of electrolyte decomposition, and generates
Water, to accelerate the deterioration of positive electrode.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of nickelic ternarys of double-coating
The preparation method of positive electrode.
To achieve the goals above or other purposes, the present invention are achieved through the following technical solutions:
A kind of preparation method of the nickelic tertiary cathode material of double-coating, includes the following steps, S1, will be before nickelic ternary
It drives body to be mixed with lithium source, and is put into high temperature furnace and calcines, nickelic tertiary cathode material is obtained, wherein before the nickelic ternary
It is 1:0.95 that body and lithium source, which are driven, by the ratio between the substance total amount of lithium in metal ion species total amount in nickelic ternary precursor and lithium source
~1.15 are matched；S2, covering is mixed and is ground with the nickelic tertiary cathode material in step S1, and be put into height
It is calcined in warm furnace, obtains compound；S3, compound and graphene nanobelt are weighed by certain mass ratio, by weighed compound
It is mixed by certain mass volume ratio with ethanol solution, obtains mixed solution A, while weighed graphene nanobelt is pressed into certain matter
Amount volume ratio is mixed with ethanol solution, obtains mixed solution B；It is 5~60 DEG C that mixed solution B, which is slowly added into whipping temp,
In mixed solution A, continues 1~30min of stirring, obtain mixed solution C；S4, mixed solution C obtained is centrifuged, dry with
And after dehydration, the nickelic tertiary cathode material of double-coating can be obtained.
The further technical solution of the present invention is, in step S1, the nickelic ternary precursor is NixCoyMn1-x-y(OH)2
(0.6≤x≤1.0) or NixCoyMn1-x-yCO3It is one of (0.6≤x≤1.0) or a variety of；The lithium source is Li2CO3、LiOH
Or CH3One of COOLi or a variety of.
The further technical solution of the present invention is, in step S2, the covering is Al2O3、TiO2、ZrO2、B2O3、V2O5、
SiO2、H3BO3And one of PVDF or a variety of.
The further technical solution of the present invention is, the mass ratio of the covering and nickelic tertiary cathode material is 0.1~
5:1000。
The further technical solution of the present invention is, the mass ratio of the covering and nickelic tertiary cathode material is 0.5~
3:1000。
The further technical solution of the present invention is, in step S3, the width of the graphene nanobelt is 3~70nm, long
Diameter ratio is 30~500.
The further technical solution of the present invention is, in step S3, the quality of the graphene nanobelt and the compound
Than for 0.1~1:1000.
The further technical solution of the present invention is, in step S3, the mass volume ratio of the compound and ethanol solution is 5
The mass volume ratio of~50g:100ml, the graphene nanobelt and ethanol solution is 0.0005~0.05g:100ml.
The further technical solution of the present invention is, in step S4, the revolving speed of the centrifugation is 2000~5000r/min, often
Secondary centrifugation time is 3~15min, it is described wash the solution that uses for deionized water, dehydrated alcohol it is one such or two kinds.
The further technical solution of the present invention is, in step S1, the temperature of the calcining is 700~900 DEG C, the time 5
~20h；In step S2, the temperature of the calcining is 300~750 DEG C, and the time is 2~8h.
The utility model has the advantages that
1, the present invention is using the nickelic tertiary cathode material with dual cladding effect as the positive material of lithium ion battery
Material significantly reduces the surface residual alkali content of lithium ion battery, reduces material surface pH value, the processing performance of material is improved, with this
Improve the safety of entire battery system；
2, the graphene nanobelt used in the present invention has good electric conductivity and fake capacitance characteristic, structural stability
By force, graphene nanobelt is closely wound and is wrapped in outer surface and has on the nickelic tertiary cathode material of covering, be remarkably improved
The structural stability and ionic conductivity of material, and then improve discharge capacity, cyclical stability and the high rate performance of material；
3, the preparation method of the nickelic tertiary cathode material of double-coating of the present invention is simple, abundant raw material, energy consumption
It is low, production technology is safe and reliable, production cost is low, be easy to large-scale production.
Detailed description of the invention
Fig. 1 be curve of double curvature figure at 0.2C, 0.33C, 0.5C, 1C, 0.2C of the embodiment of the present invention 1 and comparative example 1 and
50 cyclic curve figures under 1C.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
The preparation method of the nickelic tertiary cathode material of double-coating of the present invention includes following steps, S1, general
Nickelic ternary precursor is mixed with lithium source, and is put into high temperature furnace and is calcined, and the temperature of calcining is 700~900 DEG C, and the time is
5~20h obtains nickelic tertiary cathode material, wherein the nickelic ternary precursor is NixCoyMn1-x-y(OH)2(0.6≤x≤
Or Ni 1.0)xCoyMn1-x-yCO3One of (0.6≤x≤1.0) or a variety of, the lithium source is Li2CO3, LiOH or CH3COOLi
One of or it is a variety of, while the nickelic ternary precursor and lithium source are by metal ion species total amount in nickelic ternary precursor
It is matched with the ratio between the substance total amount of lithium in lithium source for 1:0.95~1.15, metal ion therein is Ni, Co and Mn；
S2, by covering with the nickelic tertiary cathode material in step S1 in mass ratio it is that 0.1~5:1000 is mixed and ground, and
It is put into high temperature furnace and calcines, calcination temperature is 300~750 DEG C, and the time is 2~8h, compound is obtained, wherein the covering is
Al2O3、TiO2、ZrO2、B2O3、V2O5、SiO2、H3BO3And one of PVDF or a variety of；S3, weighed by certain mass ratio it is compound
Object and graphene nanobelt, wherein the mass ratio of the graphene nanobelt and the compound is 0.1~1:1000, simultaneously
The width of the graphene nanobelt is 3~70nm, and draw ratio is 30~500；Weighed compound is pressed into mass volume ratio 5
~50g:100ml is mixed with ethanol solution, obtains mixed solution A, while weighed graphene nanobelt is pressed mass volume ratio
0.0005~0.05g:100ml is mixed with ethanol solution, obtains mixed solution B；Mixed solution B is slowly added into whipping temp
To continue 1~30min of stirring, obtaining mixed solution C in 5~60 DEG C of mixed solution As；S4, mixed solution C obtained is passed through
After centrifugation, dry and dehydration, the nickelic tertiary cathode material of double-coating can be obtained, wherein the revolving speed of the centrifugation is
2000~5000r/min, each centrifugation time are 3~15min, and the solution used that washs is deionized water, dehydrated alcohol
It is one such or two kinds.
Embodiment 1
Prepare LiNi0.8Co0.1Mn0.1O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.8Co0.1Mn0.1(OH)2It is mixed, and is put into high temperature furnace with lithium source LiOH
Calcining, the temperature of calcining are 820 DEG C, time 12h, obtain nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2, wherein institute
Nickelic ternary precursor and lithium source are stated by the substance total amount of lithium in metal ion species total amount in nickelic ternary precursor and lithium source
The ratio between matched for 1:0.99；
S2, by covering ZrO2With the nickelic tertiary cathode material in step S1 be in mass ratio 3:1000 mix and
Grinding, and be put into high temperature furnace and calcine, calcination temperature is 650 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 1:1000；Weighed compound is mixed by mass volume ratio 10g:100ml with ethanol solution, is obtained
Mixed solution A, while weighed graphene nanobelt being mixed by mass volume ratio 0.01g:100ml with ethanol solution, it obtains
Mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 25 DEG C, continues to stir 30min, obtain
Mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 4000r/min, each centrifugation time is 5min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 2
Prepare LiNi0.85Co0.05Mn0.1O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.85Co0.05Mn0.1(OH)2It is mixed with lithium source LiOH, and is put into high temperature furnace
Middle calcining, the temperature of calcining are 780 DEG C, time 12h, obtain nickelic tertiary cathode material LiNi0.85Co0.05Mn0.1O2, wherein
The nickelic ternary precursor is total by metal ion species total amount in nickelic ternary precursor and the substance of lithium in lithium source with lithium source
The ratio between amount is matched for 1:1.03；
S2, by covering Al2O3With the nickelic tertiary cathode material in step S1 be in mass ratio 1:1000 mix and
Grinding, and be put into high temperature furnace and calcine, calcination temperature is 700 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 0.5:1000；Weighed compound is mixed by mass volume ratio 20g:100ml with ethanol solution, is obtained
It mixes, obtains with ethanol solution by mass volume ratio 0.01g:100ml to mixed solution A, while by weighed graphene nanobelt
To mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 40 DEG C, continues to stir 20min, obtain
To mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 4000r/min, each centrifugation time is 5min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 3
Prepare LiNi0.85Co0.05Mn0.1O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.85Co0.05Mn0.1(OH)2It is mixed with lithium source LiOH, and is put into high temperature furnace
Middle calcining, the temperature of calcining are 780 DEG C, time 12h, obtain nickelic tertiary cathode material LiNi0.85Co0.05Mn0.1O2, wherein
The nickelic ternary precursor is total by metal ion species total amount in nickelic ternary precursor and the substance of lithium in lithium source with lithium source
The ratio between amount is matched for 1:1.05；
S2, by covering H3BO3It is in mass ratio that 0.5:1000 is mixed with the nickelic tertiary cathode material in step S1
And grinding, and be put into high temperature furnace and calcine, calcination temperature is 350 DEG C, and time 3h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 0.5:1000；Weighed compound is mixed by mass volume ratio 30g:100ml with ethanol solution, is obtained
It mixes, obtains with ethanol solution by mass volume ratio 0.015g:100ml to mixed solution A, while by weighed graphene nanobelt
To mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 50 DEG C, continues to stir 15min, obtain
To mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 4000r/min, each centrifugation time is 5min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 4
Prepare LiNi0.9Co0.05Mn0.05O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.9Co0.05Mn0.05(OH)2It is mixed with lithium source LiOH, and is put into high temperature furnace
Middle calcining, the temperature of calcining are 750 DEG C, time 12h, obtain nickelic tertiary cathode material LiNi0.9Co0.05Mn0.05O2, wherein
The nickelic ternary precursor is total by metal ion species total amount in nickelic ternary precursor and the substance of lithium in lithium source with lithium source
The ratio between amount is matched for 1:1.03；
S2, be in mass ratio by covering PVDF and the nickelic tertiary cathode material in step S1 2:1000 mixed and
Grinding, and be put into high temperature furnace and calcine, calcination temperature is 400 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 0.4:1000；Weighed compound is mixed by mass volume ratio 50g:100ml with ethanol solution, is obtained
It mixes, obtains with ethanol solution by mass volume ratio 0.02g:100ml to mixed solution A, while by weighed graphene nanobelt
To mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 60 DEG C, continues to stir 5min, obtain
To mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 4000r/min, each centrifugation time is 5min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 5
Prepare LiNi0.8Co0.1Mn0.1O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.8Co0.1Mn0.1(OH)2It is mixed, and is put into high temperature furnace with lithium source LiOH
Calcining, the temperature of calcining are 780 DEG C, time 12h, obtain nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2, wherein institute
Nickelic ternary precursor and lithium source are stated by the substance total amount of lithium in metal ion species total amount in nickelic ternary precursor and lithium source
The ratio between matched for 1:1.05；
S2, by covering TiO2With the nickelic tertiary cathode material in step S1 be in mass ratio 5:1000 mix and
Grinding, and be put into high temperature furnace and calcine, calcination temperature is 700 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 1:1000；Weighed compound is mixed by mass volume ratio 10g:100ml with ethanol solution, is obtained
Mixed solution A, while weighed graphene nanobelt being mixed by mass volume ratio 0.01g:100ml with ethanol solution, it obtains
Mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 40 DEG C, continues to stir 30min, obtain
Mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 4000r/min, each centrifugation time is 5min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 6
Prepare LiNi0.8Co0.1Mn0.1O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.8Co0.1Mn0.1(OH)2It is mixed, and is put into high temperature furnace with lithium source LiOH
Calcining, the temperature of calcining are 900 DEG C, time 10h, obtain nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2, wherein institute
Nickelic ternary precursor and lithium source are stated by the substance total amount of lithium in metal ion species total amount in nickelic ternary precursor and lithium source
The ratio between matched for 1:1.07；
S2, by covering TiO2It is in mass ratio that 0.1:1000 is mixed with the nickelic tertiary cathode material in step S1
And grinding, and be put into high temperature furnace and calcine, calcination temperature is 800 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 0.5:1000；Weighed compound is mixed by mass volume ratio 20g:100ml with ethanol solution, is obtained
It mixes, obtains with ethanol solution by mass volume ratio 0.01g:100ml to mixed solution A, while by weighed graphene nanobelt
To mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 40 DEG C, continues to stir 30min, obtain
To mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 4000r/min, each centrifugation time is 5min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 7
Prepare LiNi0.8Co0.1Mn0.1O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.8Co0.1Mn0.1(OH)2It is mixed, and is put into high temperature furnace with lithium source LiOH
Calcining, the temperature of calcining are 860 DEG C, time 18h, obtain nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2, wherein institute
Nickelic ternary precursor and lithium source are stated by the substance total amount of lithium in metal ion species total amount in nickelic ternary precursor and lithium source
The ratio between matched for 1:1.15；
S2, by covering ZrO2With the nickelic tertiary cathode material in step S1 be in mass ratio 4:1000 mix and
Grinding, and be put into high temperature furnace and calcine, calcination temperature is 500 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 0.4:1000；Weighed compound is mixed by mass volume ratio 50g:100ml with ethanol solution, is obtained
It mixes, obtains with ethanol solution by mass volume ratio 0.02g:100ml to mixed solution A, while by weighed graphene nanobelt
To mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 30 DEG C, continues to stir 25min, obtain
To mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 2000r/min, each centrifugation time is 10min, the solution that the washing uses
For dehydrated alcohol.
Embodiment 8
Prepare LiNi0.9Co0.05Mn0.05O2Composite material, the specific steps are as follows:
S1, by nickelic ternary precursor Ni0.9Co0.05Mn0.05(OH)2It is mixed with lithium source LiOH, and is put into high temperature furnace
Middle calcining, the temperature of calcining are 850 DEG C, time 20h, obtain nickelic tertiary cathode material Li Ni0.9Co0.05Mn0.05O2,
Described in nickelic ternary precursor and lithium source by lithium in metal ion species total amount in nickelic ternary precursor and lithium source substance
The ratio between total amount is that 1:0.95 is matched；
S2, by covering ZrO2With the nickelic tertiary cathode material in step S1 be in mass ratio 4:1000 mix and
Grinding, and be put into high temperature furnace and calcine, calcination temperature is 600 DEG C, and time 5h obtains compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, wherein the graphene nanobelt with it is described
The mass ratio of compound is 1:1000；Weighed compound is mixed by mass volume ratio 50g:100ml with ethanol solution, is obtained
Mixed solution A, while weighed graphene nanobelt being mixed by mass volume ratio 0.05g:100ml with ethanol solution, it obtains
Mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 20 DEG C, continues to stir 25min, obtain
Mixed solution C；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic ternary of double-coating can be obtained
Positive electrode, wherein the revolving speed of the centrifugation is 5000r/min, each centrifugation time is 3min, the solution that the washing uses
For dehydrated alcohol.
Comparative example 1
By nickelic ternary precursor Ni0.8Co0.1Mn0.1(OH)2It is mixed with lithium source LiOH, and is put into high temperature furnace and forges
It burns, the temperature of calcining is 820 DEG C, time 12h, obtains nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2, wherein described
Nickelic ternary precursor and lithium source by lithium in metal ion species total amount in nickelic ternary precursor and lithium source substance total amount it
Than being matched for 1:0.99.
Comparative example 2
By nickelic ternary precursor Ni0.8Co0.1Mn0.1(OH)2It is mixed with lithium source LiOH, and is put into high temperature furnace and forges
It burns, the temperature of calcining is 820 DEG C, time 12h, obtains nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2, wherein described
Nickelic ternary precursor and lithium source by lithium in metal ion species total amount in nickelic ternary precursor and lithium source substance total amount it
Than being matched for 1:0.99；By covering ZrO2With the nickelic tertiary cathode material in step S1 be in mass ratio 3:1000 into
Row mixing and grinding, and be put into high temperature furnace and calcine, calcination temperature is 650 DEG C, time 5h, obtains the compound of single layer cladding
Object.
Electrochemical property test is carried out to finished product made of embodiment 1-8 and comparative example 1-2, see Table 1 for details for design parameter.
Table 1
| Sample | pH | LiOH (%) | Li2CO3(%) |
| Embodiment 1 | 11.62 | 0.0790 | 0.0550 |
| Comparative example 1 | 11.98 | 0.2018 | 0.2416 |
| Comparative example 2 | 12.06 | 0.3873 | 0.1654 |
| Embodiment 2 | 11.59 | 0.0840 | 0.0461 |
| Embodiment 3 | 11.53 | 0.0784 | 0.0514 |
| Embodiment 4 | 11.49 | 0.0690 | 0.0432 |
| Embodiment 5 | 11.88 | 0.2594 | 0.1158 |
| Embodiment 6 | 11.84 | 0.1918 | 0.1553 |
| Embodiment 7 | 11.95 | 0.2308 | 0.2001 |
| Embodiment 8 | 11.90 | 0.2480 | 0.1308 |
From embodiment 1 compared with comparative example 1-2, it can be seen that after positive electrode of the invention is modified, surface residual alkali
Content is substantially reduced, and pH value is substantially reduced, show by two layers cladding after can be effectively reduced positive electrode surface residual alkali amount and
PH, improves the processing performance of material, to improve the security performance of entire battery system；Embodiment 2-8 shows energy of the present invention
Surface residual alkali amount and pH value is enough effectively reduced.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of the nickelic tertiary cathode material of double-coating, which is characterized in that include the following steps,
S1, nickelic ternary precursor is mixed with lithium source, and is put into high temperature furnace and calcines, obtain nickelic tertiary cathode material
Material, wherein the nickelic ternary precursor and lithium source are by lithium in metal ion species total amount in nickelic ternary precursor and lithium source
The ratio between substance total amount is that 1:0.95 ~ 1.15 are matched；
S2, covering is mixed and is ground with the nickelic tertiary cathode material in step S1, and be put into high temperature furnace and calcine,
Obtain compound；
S3, compound and graphene nanobelt are weighed by certain mass ratio, by weighed compound by certain mass volume ratio with
Ethanol solution mixing obtains mixed solution A, while weighed graphene nanobelt is pressed certain mass volume ratio and ethanol solution
Mixing, obtains mixed solution B；Mixed solution B is slowly added into the mixed solution A that whipping temp is 5~60 DEG C, continues to stir
1~30min is mixed, mixed solution C is obtained；
S4, by mixed solution C obtained through centrifugation, drying and dehydration after, the nickelic tertiary cathode of double-coating can be obtained
Material.
2. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1, which is characterized in that step
In S1, the nickelic ternary precursor is NixCoyMn1-x-y(OH)2 (0.6≤x≤1.0) or NixCoyMn1-x-yCO3 (0.6≤x
≤ 1.0) one of or a variety of；The lithium source is Li2CO3, LiOH or CH3One of COOLi or a variety of.
3. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1, which is characterized in that step
In S2, the covering is Al2O3、TiO2、ZrO2、B2O3、V2O5、SiO2、H3BO3And one of PVDF or a variety of.
4. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1 to 3, which is characterized in that institute
The mass ratio for stating covering and nickelic tertiary cathode material is 0.1 ~ 5:1000.
5. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 4, which is characterized in that described
The mass ratio of covering and nickelic tertiary cathode material is 0. 5 ~ 3:1000.
6. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1, which is characterized in that step
In S3, the width of the graphene nanobelt is 3~70nm, and draw ratio is 30~500.
7. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1 or 6, which is characterized in that
In step S3, the mass ratio of the graphene nanobelt and the compound is 0.1 ~ 1:1000.
8. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1, which is characterized in that step
In S3, the mass volume ratio of the compound and ethanol solution is 5~50g:100ml, and the graphene nanobelt and ethyl alcohol are molten
The mass volume ratio of liquid is 0.0005~0.05g:100ml.
9. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1, which is characterized in that step
In S4, the revolving speed of the centrifugation is 2000~5000r/min, and each centrifugation time is 3~15min, and the washing uses molten
Liquid is that deionized water, dehydrated alcohol are one such or two kinds.
10. the preparation method of the nickelic tertiary cathode material of double-coating according to claim 1, which is characterized in that step
In rapid S1, the temperature of the calcining is 700 ~ 900 DEG C, and the time is 5 ~ 20h；In step S2, the temperature of the calcining is 300 ~ 750
DEG C, the time is 2 ~ 8h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111769267A (en) * | 2020-06-30 | 2020-10-13 | 中国科学院上海微***与信息技术研究所 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111785960A (en) * | 2020-09-03 | 2020-10-16 | 中南大学 | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN113716549A (en) * | 2020-12-16 | 2021-11-30 | 山东海科创新研究院有限公司 | Multi-element coated core-shell structure lithium ion positive electrode material and preparation method thereof |
| CN113716623A (en) * | 2021-08-27 | 2021-11-30 | 中国地质大学（武汉） | High-nickel ternary material LiNi0.80Co0.15Al0.05O2Coating method of |
| CN114530580A (en) * | 2020-11-23 | 2022-05-24 | 天津国安盟固利新材料科技股份有限公司 | Preparation method of high-capacity double-coated lithium ion positive electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450174A (en) * | 2016-05-23 | 2017-02-22 | 重庆大学 | Preparation method for graphene nanobelt-lithium iron phosphate composite material |
| CN106711435A (en) * | 2016-08-17 | 2017-05-24 | 重庆大学 | Preparation method of layered lithium-manganese-rich base/GNRs (graphene nanoribbons) anode composite material |
| CN107910532A (en) * | 2017-11-20 | 2018-04-13 | 复旦大学 | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material |
| CN109244447A (en) * | 2018-09-26 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of cladded type nickle cobalt lithium manganate tertiary cathode material and its preparation method and application |
-
2019
- 2019-06-03 CN CN201910477550.5A patent/CN110176593A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450174A (en) * | 2016-05-23 | 2017-02-22 | 重庆大学 | Preparation method for graphene nanobelt-lithium iron phosphate composite material |
| CN106711435A (en) * | 2016-08-17 | 2017-05-24 | 重庆大学 | Preparation method of layered lithium-manganese-rich base/GNRs (graphene nanoribbons) anode composite material |
| CN107910532A (en) * | 2017-11-20 | 2018-04-13 | 复旦大学 | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material |
| CN109244447A (en) * | 2018-09-26 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of cladded type nickle cobalt lithium manganate tertiary cathode material and its preparation method and application |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111769267A (en) * | 2020-06-30 | 2020-10-13 | 中国科学院上海微***与信息技术研究所 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111769267B (en) * | 2020-06-30 | 2022-02-22 | 中国科学院上海微***与信息技术研究所 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111785960A (en) * | 2020-09-03 | 2020-10-16 | 中南大学 | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN111785960B (en) * | 2020-09-03 | 2020-11-20 | 中南大学 | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN114530580A (en) * | 2020-11-23 | 2022-05-24 | 天津国安盟固利新材料科技股份有限公司 | Preparation method of high-capacity double-coated lithium ion positive electrode material |
| CN113716549A (en) * | 2020-12-16 | 2021-11-30 | 山东海科创新研究院有限公司 | Multi-element coated core-shell structure lithium ion positive electrode material and preparation method thereof |
| CN113716623A (en) * | 2021-08-27 | 2021-11-30 | 中国地质大学（武汉） | High-nickel ternary material LiNi0.80Co0.15Al0.05O2Coating method of |
| CN113716623B (en) * | 2021-08-27 | 2022-07-19 | 中国地质大学（武汉） | High-nickel ternary material LiNi0.80Co0.15Al0.05O2Coating method of |
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